comparison of liquid product characteristics of pfad metal

J. Eng. Technol. Sci., Vol. 53, No. 3, 2021, 210311

Received December 2nd, 2019, Revised July 24th, 2020, Accepted for publication May 28th, 2021.

Copyright ©2021 Published by ITB Institute for Research and Community Services, ISSN: 2337-5779,

DOI: 10.5614/j.eng.technol.sci.2021.53.3.11

Comparison of Liquid Product Characteristics of PFAD

Metal Soap Decarboxylation by Batch and Continuous

Process

Lidya Elizabeth1,5, Godlief F Neonufa1,4, Endar Puspawiningtiyas1,6, Meiti

Pratiwi1,2, Astri Nur Istyami1,2, Ronny Purwadi1,3 & Tatang H Soerawidjaja1,2

1Department of Chemical Engineering, Faculty of Industrial Technology, Institut

Teknologi Bandung, Jalan Ganesa No. 10, Bandung 40132 Indonesia 2Department of Bioenergy Engineering and Chemurgy, Faculty of Industrial

Technology, Institut Teknologi Bandung, Jatinangor, Sumedang 45363 Indonesia 3Department of Food Engineering, Faculty of Industrial Technology,

Institut Teknologi Bandung, Jatinangor, Sumedang 45363 Indonesia 4Department of Agricultural Product Technology, Faculty of Agricultural Technology,

Universitas Kristen Artha Wacana, Jalan Adisoecipto No. 147, Kupang 85228 Indonesia 5Department of Chemical Engineering, Politeknik Negeri Bandung, Jalan Gegerkalong

Hilir, Ds. Ciwaruga, Kec. Parongpong, Kab. Bandung Barat 40559 Indonesia 6Department of Chemical Engineering, Universitas Muhammadiyah Purwokerto,

Jalan KH. Ahmad Dahlan, Dusun III, Kab. Banyumas, Jawa Tengah 53182 Indonesia

*E-mail: [email protected]

Highlights:

The yield from the batch process was relatively similar to that from the continuous

process.

The amount of paraffin produced by the batch process was higher than by its

continuous counterpart.

The decomposition of metal base soap with a continuous process is highly developable

due to its potential to save time and cost of bio-hydrocarbon production.

Abstract. Well-run continuous processes will benefit the industrial world in the

future. This paper investigated the effect of batch and continuous processes on

metal basic soap decarboxylation in terms of the liquid product characteristics.

The metal soap used in the process was made from palm fatty acid distillate

(PFAD) reacted with mixed metal oxides of Zn, Mg, and Ca. While the batch

decarboxylation was carried out in a batch reactor at 400 °C for 5 hours, the

continuous decarboxylation was conducted at 400 °C with a feed flow rate of 3.75

gr/minutes. Theoretically, the yield of batch decarboxylation is 76.6 wt% while

the yield of continuous decarboxylation is 73.37 wt%. The liquid product was

fractionated to separate short-chain hydrocarbon of C7-C10 (gasoline fractions)

mailto:[email protected]

Lidya Elizabeth, et al.

from medium- to long-chain hydrocarbons, or greater than C11 (green diesel

fraction). The result showed that the alkane content from the batch process was

higher than from the continuous process, whereas the continuous process produced

more ketone products compared to the batch process. Furthermore, the GC-FID

analysis showed a similar amount of total hydrocarbon (alkane, iso-alkane, and

alkene) in both the batch and the continuous process.

Keywords: batch decarboxylation; continuous decarboxylation; metal basic soap; green

diesel; bio-hydrocarbon.

1 Introduction

One of the biggest challenges in the use of oil-fat resources as diesel fuel

substitute is the presence of oxygen content; it raises the affinity of fatty acid fuel

molecules for water. Since water is a polar compound (one end is positively

charged while the other is negatively charged) it is not compatible with nonpolar

oil molecules [1]. Recently, biofuel without oxygen content, or drop-in biofuel,

has been developed to address this issue. This renewable fuel in the form of non-

oxygenated diesel fuel is called green diesel. It can be formed from fatty acids by

conventional hydroprocessing technology.

This process takes place at temperatures ranging from 600 to 700 F, pressure

ranging between 40 and 100 atm, reaction times ranging from 10 to 60 min, and

it uses catalysts. The oil-fat can be processed via hydrogenation/hydro process or

co-processing to obtain diesel fuel. It will be converted into a propane molecule

and hydrocarbon molecules in the C12 to C18 range. It does not contain sulfur

and the cetane number range is 90 to 100 [2]. The hydroprocessing technology is

an expensive method because it consumes a large amount of hydrogen [3] and

uses noble metals as catalysts [4].

Fatty acid deoxygenation is a method to obtain renewable bio-hydrocarbon.

Decarboxylation is one pathway of deoxygenation. As an example, the

decarboxylation reaction of palmitic acid is shown in Eq. (1):

C15H31COOH → n-C15H32 + CO2 (1)

Basic-soap decarboxylation is a very promising route to be developed as the basis

for a commercial decarboxylation process [5]. This is particularly true for the

decarboxylation of the basic-soap reaction shown in Eq. (2). Soap stock as the

feed of decarboxylation is the main by-product from vegetable oil refining and it

has low commercial value [6]. Besides, soaps from pyrolysis have high yields

and can be operated at lower temperature [7].

(RCOO)M(OH) →RH + MCO3 (2)

Liquid Product Characteristics of PFAD Metal Soap

M in Eq. (2) stands for alkali metal or alkaline earth metal. This reaction (Eq. (2))

can take place under atmospheric pressure. For example, the basic-soap

decarboxylation of palm kernel oils was carried out at 370 °C and atmospheric

pressure for 3 hours in a semi-batch reactor [8]. Meanwhile, calcium-based soap

decarboxylation was carried out at temperatures up to 370 °C for 5 hours in [9].

In this study, decarboxylation occurred at a temperature around 400 °C to obtain

green diesel. This is very interesting because the operating temperature is lower

than the pyrolysis temperature. For example, green diesel obtained by the

pyrolysis of brown grease soap occurred at 450 °C in [10].

The use of metal catalysts, with or without support, is one of the competitive

edges influencing the performance of thermal cracking, deoxygenation, and

decarboxylation. Thermal cracking of palm oil held in a pilot-scale batch reactor

of 143 L at 450 °C, atmospheric pressure, 15% (w/w) Na2CO3 catalyst yielded

around 60% (wt.) of organic liquid products (OLP) with long-chain lengths

between C9 and C19 hydrocarbon content at 92.84% (wt.). The hydrocarbon

consisted of 27,53% paraffin, 54.78% olefin and 10.53% naphthenic [11].

Meanwhile, the catalytic cracking of soap phase residue in the neutralization

process of palm oil was carried out in a batch reactor of 143 L at atmospheric

pressure, 440 °C, with 15% (wt.) Na2CO3 catalyst. It yielded 71.34% (wt.) of

organic liquid product (OLP), which comprised 6.69% (wt.) gasoline, 12.77%

(wt.) kerosene, 15.52% (wt.) light diesel, and 38.02% heavy diesel-like

hydrocarbons fuels according to the boiling range temperature range of fossil

fuels. The chemical compounds of OLP by GC-MS are alkenes 51.43% (wt.),

alkanes 29.94% (wt.), ketones 5.34% (wt.), etc. [6].

Deoxygenation of PFAD under reaction conditions of 3% (wt.) of

cobalt/activated carbon catalyst, 350 °C under inert N2 flow with a stirring rate

of 400 rpm yielded 71% hydrocarbon (C8-C20) [12]. Catalytic deoxygenation of

oleic acid carried out with 10% (wt.) 4Pt-8WOx/Al2O3 catalyst, n-heptane

solvent, 20 bar H2 pressure, 320 °C for 5 hours gave oleic acid conversion 100%

(mol). Product selectivity consisted of C18 67.1% (wt.), C17 31.6% (wt.) and

C10-16 1.3% (wt.) [13]. Decarboxylation of pelargonic (C9 monocarboxylic

acid) and azelaic acids (C9 dicarboxylic acid) from oxidative cleavage of oleic

acid gave 98.2 mol% n-octane and 73.1 mol% n-heptane was held at 300 °C/10

MPa and 300 °C/5 MPa (N2 pressure) with 6 mol% Pd/C for 2-3 h [14]. The use

of an alkali metal, which is better than noble or precious metals, is favorable in

decarboxylation. Zhong, et al. used nickel and zinc metal for the deoxygenation

of palmitic acid and obtained 90% pentadecane when operated at 300 °C and for

16 hours [15].

Commercialization of mixed metal oxide basic-soap decarboxylation is highly

potential because it produces a true ‘drop-in’ replacement fuel, it can use a wide


variety of feedstocks, and it minimizes infrastructure incompatibilities [16].

Various researches have been conducted in a batch or semi-batch reactor [6,8,10-

15]. Continuous hydrothermal decarboxylation of oleic acid in the presence of

activated carbon catalyst gave a conversion rate of 91% of oleic acid, 89.3%

selectivity to heptadecane when operated at 400 °C, 2 hours of space-time, water-

to-oleic acid ratio of 4:1, and pressure < 500 psi. The activated carbon was

deactivated at 45 hours time on stream [17]. Thus, the innovation of continuous

decarboxylation of metal basic soap at atmospheric pressure and without

replacement of fresh catalyst from the deactivated catalyst in this study is very

interesting. Therefore, the purpose of this study was to investigate liquid product

hydrocarbon characteristics, especially for green diesel from batch and

continuous metal basic-soap decarboxylation.

2 Experimental Research

2.1 Material

Metal mix (Ca-Mg-Zn) basic soap was used as the feedstock for decarboxylation

in both batch and continuous processes. The commercial metal mix comprising

CaO, MgO, and ZnO was of technical grade from a local product. Palm fatty acid

distillate (PFAD) was gifted by PT Tunas Baru Lampung.

2.2 Experiment

Metal basic soaps were made by fusion saponification of PFAD and mixed metal

oxides of CaO, MgO, and ZnO with a mol ratio 0.25; 0.25; 0.5, respectively.

Saponification occurred at 60-65 °C for 15 minutes. The batch decarboxylation

reaction occurred in a stainless steel reactor for 5 hours at 400 °C with 1000 gr

metal basic soaps as feedstock. Meanwhile, continuous decarboxylation occurred

in a stainless steel reactor in which metal basic soaps were fed via a screw

conveyor at constant flow rate (3.75 gr/minutes) and temperature 400 °C. Metal

basic soaps entered the reactor vertically from the top. Liquid products from both

batch and continuous decarboxylation were separated through fractional

distillation. A flowchart of the preparation and measurement method is presented

in Figure 1.

2.3 Analysis Measurement

The compositions of the PFAD and green diesel were measured using a GC-MS

Shimadzu 2010 equipped with an RTX-5 MS column with dimensions of 30 m x

0.25 mm x 0.25 μm and an AOC-20i auto-injector. The GC-MS measurement

method was as follows: one microliter of the sample was injected into the GC

with a split ratio of 1:100. The injector temperature was set to 340 °C. The


temperature of the GC oven was set as follows: the initial temperature was 40 °C,

then the temperature was raised at a rate of 5°C/min to 300 °C.

The metal basic-soap decomposition was measured by a TGA analyzer [18]

(Linseis STA Platinum Series – Simultaneous Thermal Analysis) using an

alumina crucible. The method of the TGA analyzer was as follows: the initial

temperature was 40 °C, then the temperature was raised at a rate of 20K/min to

1000 °C. This TGA analyzer could measure mass (TG) and energy (DTA/DSC)

changes simultaneously in a temperature range from 150 to 1750 °C.

Figure 1 Block diagram of the preparation and measurement methods.

Hydrocarbons of green diesel were also measured using a Shimadzu GC-FID

apparatus equipped with an RTX-1 FID column. The GC-FID measurement was

conducted as follows: one microliter of the sample was injected into the GC with

a split ratio of 1:100. The injector and detector temperature were set to 340 °C.


First, the temperature of the GC oven was set to an initial temperature of 40 °C.

Subsequently, the temperature was raised at a rate of 5 °C/min to 300 °C. Finally,

the temperature was raised to 315 °C at a rate of 1 °C/min.

3 Result and Discussion

3.1 Palm Fatty Acid Distillate (PFAD)

The PFAD composition was analyzed by GC-MS Shimadzu 2010, as shown in

Table 1. Table 1 shows that the PFAD comprised of both saturated and

unsaturated fatty acids. Palmitic acid (40.15 %-area) and oleic acid (40.32 %-

area) were the main fatty acids of the PFAD.

Table 1 PFAD composition.

N

o Fatty acid %-area

1 Myristic acid (C14:0) 1.68

2 Palmitic acid (C16:0) 40.15

3 Linoleate acid (C18:2) 5.16

4 Oleic acid (C18:1) 40.32

5 Stearic acid (C18:0) 7.82

6 Methyl 18-methylnonadecanoate 1.32

7 Others 3.55

Total 100

3.2 Metal Basic Soap

Table 1 shows that the PFAD comprised of both saturated and unsaturated fatty

acids. The main composition of PFAD was palmitic acid (40.15 %-area) and oleic

acid (40.32 %-area). Metal basic soap was the feed for batch and continuous

decarboxylation. It was made by a fusion process of metal oxide mix of Mg, Ca,

and Zn with a ratio of 0.25, 0.25, and 0.5 respectively. The metal basic soaps were

analyzed using thermal gravimetric analysis (TGA) to investigate the

decomposition temperature. The TGA analysis result of the metal basic soaps is

shown in Figure 2.


Figure 2 TGA analysis of the metal basic soaps.

The TGA analysis showed that the decomposition temperature range was

approximately 275 to 450 °C. This indicates that 400 °C was an appropriate

temperature for decarboxylation in this study.

3.3 Decarboxylation

While the batch decarboxylation was carried out at 400 °C for 5 hours, the

continuous decarboxylation was carried out at the same temperature with a feed

flow rate of 3.75 gram/minute. The yield of the decarboxylation process is shown

in Table 2, while the calculation is presented in Eq. (3).

𝑦𝑖𝑒𝑙𝑑 𝑜𝑓 𝑑𝑒𝑐𝑎𝑟𝑏𝑜𝑥𝑦𝑙𝑎𝑡𝑖𝑜𝑛 =𝑎𝑐𝑡𝑢𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

𝑡ℎ𝑒𝑜𝑟𝑖𝑡𝑖𝑐𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡× 100% (3)

Table 2 Decarboxylation yield.

Yield (%-Wt.)

Batch Continuous

79.68 74.31

74.05 64.38

73.53 66.23

83.77 78.09

72.00 83.83

76.60 ± 4.95 73.37 ± 8.13

The theoretical weight of the liquid product is the maximum weight of the liquid

product (RH) calculated based on the stoichiometry of the decarboxylation

reaction equation (Eq. (2)).

0

20

40

60

80

100

0 100 200 300 400 500 600 700 800 900 1000

% w

eig

ht

temperature (oC)


The yield of metal basic-soap decarboxylation, both batch and continuous, was

quite similar and higher than the thermal cracking of palm oil [11], the thermal

cracking of soap phase residue of neutralization process of palm oil [6], and the

deoxygenation of PFAD [12]. However, it was lower than hydro-processed

rapeseed oil (83% (wt.)) [8]. Although the yield is not as high, the metal basic-

soap decarboxylation process does not consume hydrogen and can be conducted

under atmospheric pressure.

Metal basic-soap decarboxylation generated a liquid product consisting of

kerosene, diesel, and heavy fuel fraction. To separate these three components,

they were treated using fractional distillation. The kerosene fraction was obtained

at a temperature of 180 to 200 °C, while the diesel fraction was obtained at a

temperature 270 to 350 °C. The rest of the liquid products were heavy fractions.

The diesel fraction or green diesel was analyzed by GC-FID Shimadzu 2010. The

GC-FID chromatogram is shown in Figure 3.

Figure 3 GC-FID chromatogram of green diesel from batch and continuous

decarboxylation.


The peak of the GC-FID chromatogram in Figure 3 indicates alkane, alkene, and

iso alkane. Figure 4 shows the coincident long carbon chain range (C9 to C19)

from batch and continuous decarboxylation.

The variety of carbon chain lengths produced in this process was between C10

and C20. This is because the metal not only selective forms C15 (as main

decarboxylation product of palmitic acid) but also generates cracking to form

shorter carbon chain lengths (<C15). In addition, there is a tendency for

polymerization after decarboxylation of oleic acid. When C18 has formed C17

(decarboxylation product of oleic acid), soon after the C17 captures shorter

molecules (from the cracking process) to form C19 molecules. The difference in

liquid product quantity (wt%) from the batch and the continuous decarboxylation

can be seen in the C15 and C19 carbon chains.

Figure 4 illustrates that the amount of C15 carbon chains obtained from the batch

process was higher compared to the continuous process. However, the amount of

C19 carbon chains obtained from the continuous process was higher than from

the batch one. Figure 4 also shows that C15 was the main product of green diesel.

This is because the main fatty acid of PFAD is palmitic acid.

Figure 4 Carbon chain distribution of green diesel from batch and continuous

decarboxylation.

As expressed in Eq. (2), palmitic basic soap generates pentadecane through

decarboxylation. The other main fatty acid of PFAD is oleic acid. Oleic basic

soap produces various short and long carbon chains since it is an unsaturated fatty

acid.

The composition of green diesel was also analyzed in more detail by GC-MS.

The results are shown in Figure 5 and Tables 3 to 4.


Figure 5 GC-MS chromatogram of green diesel.

Table 3 Hydrocarbon components of green diesel from batch decarboxylation.

Carbon

chain Compounds % Area Compounds % Area

Alkane Alkenes

C11 Undecane 3.84 1-undecene 3.53

C12 Dodecane 5.25 2-dodecene 3.94

C13 Tridecane 10.24 1-tridecene 5.43

C14 Tetradecane 7.04 1-tetradecene 12.2

C15 Pentadecane 15.87 1-pentadecene 7.14

C16 Hexadecane 3.03 1-hexadecene 2.53

C17 Heptadecane 3.26

Ketone Cyclic

C11 Octyl-cyclopropane 2

C12 Nonyl-cyclopropane 1.09

C14 Cyclotetradecane 1.37

C15 Nonyl cyclohexane 1.37

C16 Cyclohexene, 1-nonyl 1.24

C17 2-Heptadecanone 8.2

C18 4-Octadecanone 1.43

min

batch

continuous


Table 4 Hydrocarbon components of green diesel from continuous

decarboxylation.

Carbon

chain Alkane % Area Alkene % Area

Alkane Alkene

C11 Undecane 3.52 1-undecene 5.38

C12 Dodecane 3.96 1-dodecene 5.05

C13 Tridecane 8.44 1-tridecene 5.66

C14 Tetradecane 4.11 1-tetradecene 14.14

C15 Pentadecane 9.32 1-pentadecene 8.16

C16 Hexadecane 1.89 1-hexadecene 2.83

C17 Heptadecane 1.96

Ketone Cyclic

C8 2-Octanone 2.04

C10 2-Decanone 2.53

C11 2-Undecanone 1.37 Octyl-cyclopropane 2.81

C12 Nonyl-cyclopropane 1.60

C17

2-

Heptadecanone 13.38

C18 4-Octadecanone 1.87

Tables 3 and 4 show that the green diesel from both batch and continuous

decarboxylation contained alkane, alkene, ketone, and cyclic compounds.

Pentadecane (15.87 %-area) and 1-tetradecane (12.2 %-area) were the main

compounds of green diesel from batch decarboxylation. For the green diesel from

the continuous process, 1-tetradecane (14.14 %-area) and pentadecane (9.32 %-

area) were also the main compounds. The main liquid products from both GC-

FID and GC-MS analyses were similar.

Figure 6 offers a specific comparison of the green diesel resulted from batch and

continuous decarboxylation. The amount of green diesel paraffin (alkane) from

the batch process was higher than from the continuous one. Meanwhile, the

amount of olefin (alkene) in the green diesel from the continuous process was

higher compared to its batch counterpart.

Reactions occurring in Ca soap pyrolysis from vegetable oil are decarboxylation,

cracking, dehydrogenation, cyclization, hydrogenation, and olefin

polymerization [19]. Therefore, the reaction pathway in the batch reactor perhaps

started with decarboxylation, followed by cracking into a shorter olefin

compound. Afterward, the olefin compound turned into paraffin through

hydrogenation.


Figure 6 Type of green diesel hydrocarbon from batch and continuous

decarboxylation.

Similarly, the reaction pathway in the continuous reactor also started with

decarboxylation and continued with cracking into olefin compounds. However,

the reaction did not resume with hydrogenation. This only occurred because the

resident time in the batch reactor was much longer (5 hours) than in the

continuous reactor. Therefore, the reactions in the batch reactor took place

simultaneously and were more complex than in the continuous reactor.

There are two reasons for the generation of ketone products. Firstly, free fatty

acids in basic soaps are catalyzed by MgO to form ketones at temperatures over

340 °C [20]. Secondly, ketones are formed by stoichiometric soap

decarboxylation. As decarboxylation feedstock, metal basic soaps still contain

stoichiometric soaps. The reaction is presented in Eq. (4):

M(R1COO)2 + M(R2COO)2 → 2R1-CO-R2 (4)

The amount of ketone from the continuous process was higher than from the batch

decarboxylation. This is because the batch process was carried out in a closed

system, whereas continuous decarboxylation was carried out in an open system.

This continuous reactor allows for air contamination since the feeding system is

open.

The presence of olefins and ketones is unstable in fuel drops. Olefin does not

contribute to the cetane number and ketones are oxygenated fuel. Hence, further

investigation of continuous decarboxylation is necessary due to its potential use

in the commercialization of liquid bio-hydrocarbon production. Also, further

research to reduce the content of ketones and olefins in drop-in fuels is necessary.

0

10

20

30

40

50

60

batch continuos

com

po

siti

on

(%

-are

a)

type of hydrocarbon

parafin

olefin

ketone

cyclic


It is recommended that the research should focus on modifying the base-soap feed

system into a continuous reactor by equipping the reactor with a hot melt

extruder. The presence of the hot melt extruder can prevent the entry of oxygen

from the surrounding air into the continuous process feed, which can trigger the

formation of ketone and olefin compounds.

4 Conclusion

Theoretically, the yield from the batch process (76.6 wt%) was relatively similar

to that from the continuous process (73.37 wt%). The amount of C15 carbon

chains in the batch process was higher compared to the continuous process. In

contrast, the quantity of C19 carbon chains produced by the continuous process

was higher than the batch one. Also, the amount of paraffin generated by the batch

process was higher than its continuous counterpart. Furthermore, the amount of

ketones from the continuous process was higher than from the batch

decarboxylation. In fact, the reactions in a batch reactor occur simultaneously and

are more complex than in a continuous reactor.

The decomposition of metal base soap with a continuous process is highly

developable due to its potential to save time and cost in bio-hydrocarbon

production. Modification of the continuous reactor by adding a hot melt extruder

is recommended to reduce ketones and olefins in the drop-in fuel product. The

development of process automation as well as more detailed mass and energy

balance calculations for the continuous decarboxylation process are also

necessary to improve the effectiveness and efficiency of the decarboxylation

process.

Acknowledgement

This study was supported by the Indonesian Oil Palm Plantations Fund

Management Agency (BPDPKS) under GRS-16.

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